CN105399787A - Method for extracting hesperidin, neohesperidin and synephrine from citrus peel and citrus fruits - Google Patents
Method for extracting hesperidin, neohesperidin and synephrine from citrus peel and citrus fruits Download PDFInfo
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- CN105399787A CN105399787A CN201510892989.6A CN201510892989A CN105399787A CN 105399787 A CN105399787 A CN 105399787A CN 201510892989 A CN201510892989 A CN 201510892989A CN 105399787 A CN105399787 A CN 105399787A
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- synephrine
- neohesperidin
- hesperidin
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- YRCWQPVGYLYSOX-UHFFFAOYSA-N synephrine Chemical compound CNCC(O)C1=CC=C(O)C=C1 YRCWQPVGYLYSOX-UHFFFAOYSA-N 0.000 title claims abstract description 78
- ARGKVCXINMKCAZ-UHFFFAOYSA-N neohesperidine Natural products C1=C(O)C(OC)=CC=C1C1OC2=CC(OC3C(C(O)C(O)C(CO)O3)OC3C(C(O)C(O)C(C)O3)O)=CC(O)=C2C(=O)C1 ARGKVCXINMKCAZ-UHFFFAOYSA-N 0.000 title claims abstract description 76
- ARGKVCXINMKCAZ-UZRWAPQLSA-N neohesperidin Chemical compound C1=C(O)C(OC)=CC=C1[C@H]1OC2=CC(O[C@H]3[C@@H]([C@@H](O)[C@H](O)[C@@H](CO)O3)O[C@H]3[C@@H]([C@H](O)[C@@H](O)[C@H](C)O3)O)=CC(O)=C2C(=O)C1 ARGKVCXINMKCAZ-UZRWAPQLSA-N 0.000 title claims abstract description 39
- 229960003684 oxedrine Drugs 0.000 title claims abstract description 39
- 239000001100 (2S)-5,7-dihydroxy-2-(3-hydroxy-4-methoxyphenyl)chroman-4-one Substances 0.000 title claims abstract description 37
- QUQPHWDTPGMPEX-UHFFFAOYSA-N Hesperidine Natural products C1=C(O)C(OC)=CC=C1C1OC2=CC(OC3C(C(O)C(O)C(COC4C(C(O)C(O)C(C)O4)O)O3)O)=CC(O)=C2C(=O)C1 QUQPHWDTPGMPEX-UHFFFAOYSA-N 0.000 title claims abstract description 37
- QUQPHWDTPGMPEX-UTWYECKDSA-N aurantiamarin Natural products COc1ccc(cc1O)[C@H]1CC(=O)c2c(O)cc(O[C@@H]3O[C@H](CO[C@@H]4O[C@@H](C)[C@H](O)[C@@H](O)[C@H]4O)[C@@H](O)[C@H](O)[C@H]3O)cc2O1 QUQPHWDTPGMPEX-UTWYECKDSA-N 0.000 title claims abstract description 37
- APSNPMVGBGZYAJ-GLOOOPAXSA-N clematine Natural products COc1cc(ccc1O)[C@@H]2CC(=O)c3c(O)cc(O[C@@H]4O[C@H](CO[C@H]5O[C@@H](C)[C@H](O)[C@@H](O)[C@H]5O)[C@@H](O)[C@H](O)[C@H]4O)cc3O2 APSNPMVGBGZYAJ-GLOOOPAXSA-N 0.000 title claims abstract description 37
- VUYDGVRIQRPHFX-UHFFFAOYSA-N hesperidin Natural products COc1cc(ccc1O)C2CC(=O)c3c(O)cc(OC4OC(COC5OC(O)C(O)C(O)C5O)C(O)C(O)C4O)cc3O2 VUYDGVRIQRPHFX-UHFFFAOYSA-N 0.000 title claims abstract description 37
- QUQPHWDTPGMPEX-QJBIFVCTSA-N hesperidin Chemical compound C1=C(O)C(OC)=CC=C1[C@H]1OC2=CC(O[C@H]3[C@@H]([C@@H](O)[C@H](O)[C@@H](CO[C@H]4[C@@H]([C@H](O)[C@@H](O)[C@H](C)O4)O)O3)O)=CC(O)=C2C(=O)C1 QUQPHWDTPGMPEX-QJBIFVCTSA-N 0.000 title claims abstract description 37
- 229940025878 hesperidin Drugs 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 20
- 235000020971 citrus fruits Nutrition 0.000 title abstract description 6
- 241000207199 Citrus Species 0.000 title abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000007788 liquid Substances 0.000 claims abstract description 31
- 239000011347 resin Substances 0.000 claims abstract description 29
- 229920005989 resin Polymers 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 22
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 19
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 19
- 150000001768 cations Chemical class 0.000 claims abstract description 19
- 238000001953 recrystallisation Methods 0.000 claims abstract description 19
- 239000000047 product Substances 0.000 claims abstract description 17
- 238000002425 crystallisation Methods 0.000 claims abstract description 16
- 230000008025 crystallization Effects 0.000 claims abstract description 16
- 238000005406 washing Methods 0.000 claims abstract description 16
- 238000001556 precipitation Methods 0.000 claims abstract description 4
- 230000001105 regulatory effect Effects 0.000 claims abstract 2
- 239000000706 filtrate Substances 0.000 claims description 28
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 22
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 22
- 239000012043 crude product Substances 0.000 claims description 19
- 235000013399 edible fruits Nutrition 0.000 claims description 19
- 239000000284 extract Substances 0.000 claims description 19
- 240000004307 Citrus medica Species 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- 230000000694 effects Effects 0.000 claims description 12
- 239000006210 lotion Substances 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 11
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 10
- 239000013078 crystal Substances 0.000 claims description 10
- 230000002378 acidificating effect Effects 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 7
- 238000002203 pretreatment Methods 0.000 claims description 7
- 108010059820 Polygalacturonase Proteins 0.000 claims description 6
- 239000012141 concentrate Substances 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 5
- 239000011780 sodium chloride Substances 0.000 claims description 5
- 241001672694 Citrus reticulata Species 0.000 claims description 4
- 238000002242 deionisation method Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 238000004458 analytical method Methods 0.000 claims description 3
- 230000005089 fruit drop Effects 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000003463 adsorbent Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000010298 pulverizing process Methods 0.000 claims description 2
- 239000003513 alkali Substances 0.000 abstract description 3
- 238000001179 sorption measurement Methods 0.000 abstract description 3
- 235000019441 ethanol Nutrition 0.000 abstract 3
- 238000005325 percolation Methods 0.000 abstract 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 abstract 1
- 244000183685 Citrus aurantium Species 0.000 abstract 1
- 235000007716 Citrus aurantium Nutrition 0.000 abstract 1
- 239000002253 acid Substances 0.000 abstract 1
- 229940079593 drug Drugs 0.000 abstract 1
- 239000003814 drug Substances 0.000 abstract 1
- 239000002244 precipitate Substances 0.000 abstract 1
- 238000000967 suction filtration Methods 0.000 description 13
- 238000000605 extraction Methods 0.000 description 12
- 230000000274 adsorptive effect Effects 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 2
- 235000011130 ammonium sulphate Nutrition 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 108010093305 exopolygalacturonase Proteins 0.000 description 2
- 229930003944 flavone Natural products 0.000 description 2
- 235000011949 flavones Nutrition 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000002137 ultrasound extraction Methods 0.000 description 2
- 240000002319 Citrus sinensis Species 0.000 description 1
- 235000005976 Citrus sinensis Nutrition 0.000 description 1
- VSRVRBXGIRFARR-CIYSLCTESA-N Neohesperidose Natural products O([C@@H]1[C@@H](O)[C@H](O)[C@H](CO)O[C@H]1O)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@H](C)O1 VSRVRBXGIRFARR-CIYSLCTESA-N 0.000 description 1
- 238000000944 Soxhlet extraction Methods 0.000 description 1
- GAMYVSCDDLXAQW-AOIWZFSPSA-N Thermopsosid Natural products O(C)c1c(O)ccc(C=2Oc3c(c(O)cc(O[C@H]4[C@H](O)[C@@H](O)[C@H](O)[C@H](CO)O4)c3)C(=O)C=2)c1 GAMYVSCDDLXAQW-AOIWZFSPSA-N 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 229930013930 alkaloid Natural products 0.000 description 1
- VSRVRBXGIRFARR-OUEGHFHCSA-N alpha-L-rhamnopyranosyl-(1->2)-beta-D-glucopyranose Chemical compound O[C@@H]1[C@H](O)[C@@H](O)[C@H](C)O[C@H]1O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1O VSRVRBXGIRFARR-OUEGHFHCSA-N 0.000 description 1
- 229940088623 biologically active substance Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- -1 flavone compounds Chemical class 0.000 description 1
- 150000002213 flavones Chemical class 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 229930182478 glucoside Natural products 0.000 description 1
- 150000008131 glucosides Chemical class 0.000 description 1
- AIONOLUJZLIMTK-AWEZNQCLSA-N hesperetin Chemical compound C1=C(O)C(OC)=CC=C1[C@H]1OC2=CC(O)=CC(O)=C2C(=O)C1 AIONOLUJZLIMTK-AWEZNQCLSA-N 0.000 description 1
- 229960001587 hesperetin Drugs 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- VHBFFQKBGNRLFZ-UHFFFAOYSA-N vitamin p Natural products O1C2=CC=CC=C2C(=O)C=C1C1=CC=CC=C1 VHBFFQKBGNRLFZ-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Landscapes
- Medicines Containing Plant Substances (AREA)
- Saccharide Compounds (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
The invention discloses a method for extracting hesperidin, neohesperidin and synephrine from citrus peel and citrus fruits. Small immature bitter oranges are dried, smashed and extracted in a percolation mode. Medicine residues are extracted through alkali liquor, extracting liquid is regulated through acid and precipitates, precipitation is washed and dissoloved through 70% of ethyl alcohol, crystallized and re-crystallized, and then hesperidin products are obtained. Percolation liquid passes a strong-acidity styrene type cation column and is washed in water, enters a large-hole adsorption resin column, is washed in water, and is washed through 20% low-carbon alcohol and 70% low-carbon alcohol, washing liquid is concentrated, separated out in an assisting mode, crystallized and re-crystallized, and neohesperidin products are obtained. Percolation liquid passes a large-hole adsorption resin column, passes a strong-acidity styrene type cation column, enters a large-hole resin column and is eluted through ammonia water, crystallization and re-crystallization are performed, and then synephrine products are obtained. All the steps of crystallization and re-crystallization are performed at 5-10 DEG C.
Description
Technical field
The present invention relates to field of plant extraction, especially a kind of method extracting flavones from dried immature fruit of citron orange fruitlet.
Background technology
Oranges and tangerines are the important plants of Rutaceae Citrus, and mainly utilize its pulp and seldom fully utilize effect and pericarp, great majority are taken as waste reclamation process.Because citrus fruit, skin contain more biologically active substance, therefore more and more extensive to its utilization.Hesperidin (Hesperidin) is the natural flavone compounds in orange peel, and the Hesperidin purity adopting alkali leaching acid-precipitation method to extract from navel orange is 80.3%, and yield is 1.55%.Neohesperidin (Neohesperidin) is the glucosides formed by Hesperitin and neohesperidose, and the method extracting neohesperidin at present comprises ultrasound assisted extraction method, soxhlet extraction and water-bath reflux extraction.Synephrine (Synephrine) is the main component of dried immature fruit of citron orange alkaloids substance, and the content of synephrine reduces along with the maturation of citrusfruit, therefore generally chooses green fruit and shedding and is used as extracting raw material; The extracting method of synephrine has heating reflux method, ultrasonic extraction and microwave loss mechanisms.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of method of efficient extraction and isolation Hesperidin, neohesperidin and synephrine simultaneously from dried immature fruit of citron orange fruitlet and peel of Citrus reticulata Blanco, dried immature fruit of citron orange fruitlet is dry, pulverizing, seepage pressure effects, then slag of getting it filled carries out Hesperidin extraction, gets percolate and carries out neohesperidin and synephrine extraction; Obtain content of hesperidin and can reach 95%, yield is more than 4.0%; Neohesperidin extractive content can reach 98%, and yield is more than 2.0%, and synephrine extractive content can reach 90%, and yield is more than 2.5%.In order to solve this technical problem, the concrete implementation step of this patent is as follows:
One, bigarabe dried immature fruit of citron orange fruitlet pre-treatment
Collect dried immature fruit of citron orange fruitlet dry, pulverize, sieving, be placed in extractor, at 40-45 DEG C, use 35-50% aqueous ethanolic solution, is 1:(10-20 according to solid-liquid ratio) ratio carry out seepage pressure effects, seepage pressure effects 10-12h; Then add the polygalacturonase of 0.01-0.1%, stir 30min at 50 DEG C, then temperature is transferred to 70 DEG C, process 15-30min, kills polygalacturonase; Then filter, the dregs of a decoction are separated with filtrate; The dregs of a decoction are used for Hesperidin and extract, and filtrate is used for the extraction of neohesperidin and synephrine.
The described screen cloth sieved is 10 orders or 60 orders or 100 orders;
Described seepage pressure effects can carry out 3 times.
Two, Hesperidin extracting and developing, purifying
Be 1:(5-10 by the above-mentioned dregs of a decoction by solid-liquid ratio), be 10.0-11.0 dipping by lye by pH value, extract 0.5-1h; It is 2.0-3.0 that gained extracting solution HCl is adjusted to pH value, 5-10 DEG C of placement, and precipitation; Precipitation washed with water, be washed till neutrality, then dissolve by 70% low-carbon alcohol, being adjusted to pH value with HCl is 4.0-5.0, and 5-10 DEG C of placement, after recrystallization, washing, drying are Hesperidin product.In this product, content of hesperidin can reach 95.0%, and Hesperidin yield is more than 4.0%.
Described alkali lye is Ca (OH)
2or NaOH;
Described low-carbon alcohol is methyl alcohol or ethanol.
Three, neohesperidin extracting and developing, purifying
The filtrate of getting described in step one crosses strongly acidic styrene's type cation seperation column, and collection of ions post effluent liquid, then washes with water.By ion column effluent liquid and water lotion mixing, enter macroporous adsorptive resins, first wash with water, then with 20% low-carbon alcohol washing, then use 70% low-carbon alcohol wash-out; Get 70% low-carbon alcohol elutriant to concentrate, 5-10 DEG C of placement, add (NH by the ratio of concentrated solution quality 5.0%
4)
2sO
4/ NaCl helps and analyses, and obtains crude product; By crude product with the ratio of solid-liquid ratio 1:5g/mL, with 70% low-carbon alcohol dissolve, 5-10 DEG C of placement, recrystallization, gained crystal is neohesperidin product.In this product, content of hesperidin can reach 98.0%, and Hesperidin yield is more than 2.0%.
When neohesperidin crude product dissolves with 70% low-carbon alcohol solution, activated carbon decolorizing can also be added while stirring, while hot suction filtration, at recrystallization after cooling;
Described strongly acidic styrene's type cation seperation column preferably 001 × 7 cation seperation column;
The preferred D101 of described macroporous adsorbent resin;
Described low-carbon alcohol particular methanol or ethanol.
Four, extracting and developing, the purifying of synephrine
Get the filtrate described in step one, being adjusted to pH value with HCl is 1.0-2.0, first crosses D101 macroporous resin column, and washing is collected effluent liquid and water lotion, concentrated; Then add diatomite and carry out suction filtration, the filtrate obtained by suction filtration joins strongly acidic styrene's type cation seperation column, and entering post amount is 2BV, releases effluent liquid with flow velocity 2BV/h; Again with 2BV deionization washing resin column, release water lotion, in resin, add 1.5BV1.5mol/L ammoniacal liquor wash-out, flow velocity is 1BV/h, collect ammoniacal liquor elutriant, concentrated, being adjusted to pH value with HCl is 2.0-3.0, after D101 macroporous resin column, with 1.5mol/L ammoniacal liquor wash-out, get elutriant concentrated after, 5-10 DEG C of placement, crystallization, obtains coarse crystal; By coarse crystal dissolving with hydrochloric acid, then use 1.5mol/L ammoniacal liquor adjust pH, then concentrate, then 5-10 DEG C of placement, recrystallization, gained crystal is synephrine product, and in this product, synephrine content reaches more than 90.0%, and synephrine yield reaches more than 2.5%.
Described strongly acidic styrene's type cation seperation column preferably 001 × 7 cation seperation column;
The preferred D101 of described macroporous resin;
All crystallizations, recrystallization are all carried out below 5-10 DEG C.
Described diacolation, extraction, filtration, fractionation by adsorption, wash-out, crystallization, recrystallization are all known technology.
The present invention has following advantages and characteristic:
1, dried immature fruit of citron orange fruitlet resource is fully utilized
From the dregs of a decoction after dried immature fruit of citron orange fruitlet seepage pressure effects, extract Hesperidin, extract neohesperidin, synephrine in filtrate, achieve Hesperidin, neohesperidin, the extraction of synephrine simultaneous synthesis, dried immature fruit of citron orange fruitlet resource is fully utilized.
2, combination technique is novel
By the technical program, after dried immature fruit of citron orange fruitlet seepage pressure effects, from the dregs of a decoction, extract Hesperidin, extract neohesperidin, synephrine from filtrate, obtain content of hesperidin and reach more than 95%, yield is more than 4.0%; Obtain neohesperidin extractive content and can reach more than 98%, yield is more than 2.0%, and synephrine extractive content can reach more than 90%, and yield can reach more than 2.5%.Especially the high efficiency extraction of neohesperidin extraction and synephrine, be utilize seepage pressure effects filtrate, neohesperidin first adopts positively charged ion chromatography column, use D101 macroporous resin column again, then adopt 20% low-carbon alcohol washing, then use 70% low-carbon alcohol wash-out, get elutriant to concentrate, with (NH
4)
2sO
4/ NaCl helps and analyses, and obtains coarse-grain; Coarse-grain is dissolved by 70% low-carbon alcohol again, obtains product through recrystallization.Synephrine is that seepage pressure effects filtrate is first crossed D101 macroporous resin column, then crosses 001 × 7 cation seperation column, uses ammoniacal liquor wash-out; Use HCl adjust pH, after D101 macroporous resin column, use ammoniacal liquor wash-out, elutriant is concentrated, crystallization, recrystallization, obtains synephrine product.All crystallizations, re-crystallization step are all carry out at 5-10 DEG C.These technical characteristics are combined, and neohesperidin and synephrine extract create beyond thought effect on content and yield 2 indexs.These results are that each technical characterstic of technical combinations scheme kind is supported mutually, acting in conjunction just realizes, and known technology is not reported, also the technology of this Welded joint is not enlightened, and is not simple superposition, have outstanding substantive distinguishing features and significant progress.
Embodiment
The following stated example understands the present invention in detail.
Embodiment 1
The pre-treatment of bigarabe dried immature fruit of citron orange fruitlet
Using the dried immature fruit of citron orange fruitlet of bigarabe third time physiological fruit drop as extraction raw material, dry, pulverize with high-speed multifunctional pulverizer, get crushed material and cross 10 object sieves, accurately take crushed material 25.0g and be placed in beaker, add the aqueous ethanolic solution of 250mL35% with solid-liquid ratio 1:10g/mL, soak water-bath at putting into water-bath 40 DEG C and extract 12h, filter.Ratio with 0.05% adds 0.125g pectinase treatment in extracting solution, stirs 30min at 50 DEG C, then water-bath is adjusted to 70 DEG C, and process 15min, by abundant for polygalacturonase deactivation.Cooling, then tentatively filter with gauze, use double-layer filter paper suction filtration, obtain filtrate and filter residue, filter residue is for extracting Hesperidin, and filtrate is for extracting neohesperidin and synephrine.
Hesperidin extracts
Get above-mentioned filter residue, add water by solid-liquid ratio 1:30, at 30 DEG C, add 1.75gCa (OH) while stirring
2, now pH is 10.6, stirs after extracting 1h and filters; Get filtrate, add appropriate hydrochloric acid, adjust system pH to be 3.0, at 5-10 DEG C of standing 12h; Crystallize out, suction filtration, dries to obtain Hesperidin crude product.Add methyl alcohol with solid-liquid ratio 1:60g/mL, at adjusting system pH to be 11.0,30 DEG C by NaOH solution, react 30min, natural filtration, adjust filtrate pH to be 5.0 with dilute hydrochloric acid again, below 5-10 DEG C, leave standstill 12h, recrystallization, obtain Hesperidin crystal, the content of Hesperidin is 95.70%, and yield is 4.16%.
Neohesperidin is extracted
Get pre-treatment filtrate and cross 001 × 7 strongly acidic styrene's type cation seperation column, collection of ions post effluent liquid, then washes with water.By ion column effluent liquid and water lotion mixing, cross D101 macroporous adsorptive resins, washing, uses 20% ethanol and 70% ethanol gradient elution successively.Collect 70% ethanol eluate, be condensed into medicinal extract.Add the ammonium sulfate/solid sodium chloride of medicinal extract 5% massfraction, heat while stirring, after boiling, stop heating, cooling; At 5-10 DEG C of crystallization 12h, obtain neohesperidin crude product.Neohesperidin crude product is placed in the beaker of clean dried, in beaker, adds 70% ethanolic soln with the ratio of solid-liquid ratio 1:5g/mL, stir evenly, put into electric mantle to be heated to boil, close electric mantle, add 2g gac while stirring, beaker is taken out, while hot suction filtration, cooling after 10min; The off-white color needle-like crystal of crystallization below 5-10 DEG C; Suction filtration, dries, obtains neohesperidin; Recording purity through HPLC is 98.67%, neohesperidin yield 2.26%.
Synephrine extracts
Get pre-treatment filtrate, pH is adjusted to be 1.0 with HCl, cross D101 macroporous adsorptive resins, washing, collect effluent liquid and water lotion, concentrated, suction filtration is carried out under diatomaceous assisting, filtrate joins 001 × 7 cation seperation column after pretreatment, entering post amount is 2BV, effluent liquid is released with flow velocity 2BV/h, again with 2BV deionization washing resin column, release water lotion, 1.5BV1.5mol/L ammoniacal liquor wash-out is added in resin, flow velocity is 1BV/h, collect ammoniacal liquor elutriant, concentrated in Rotary Evaporators, being adjusted to pH value with HCl is 2.0, after D101 macroporous resin column, be 10.0 ammoniacal liquor wash-outs with pH, get elutriant concentrated after, place, 5-10 DEG C of crystallization, obtain crude product, be the HCl dissolving of 2.0 by crude product pH, then adjust pH to be 10.0 with ammoniacal liquor, then concentrate, cooling, at 5-10 DEG C of recrystallization, gained crystal is synephrine product, and in this product, synephrine content reaches more than 90.0%, and synephrine yield reaches more than 2.5%.
Embodiment 2
The pre-treatment of bigarabe dried immature fruit of citron orange fruitlet
Using the dried immature fruit of citron orange fruitlet of bigarabe third time physiological fruit drop as extraction raw material, dry, pulverize with high-speed multifunctional pulverizer, get crushed material and cross 100 object sieves, accurately take crushed material 100.0g and be placed in beaker, add the aqueous ethanolic solution of 1000mL50% with solid-liquid ratio 1:10g/mL, after stirring, put into seepage pressure effects 10h at water-bath 44 DEG C, filter.Add 0.1g pectinase treatment, at 50 DEG C, stir 30min, then water-bath is adjusted to 70 DEG C, process 30min.After its cooling, first use gauze coarse filtration, then use double-layer filter paper suction filtration, obtain filtrate and filter residue, filter residue is for extracting Hesperidin, and filtrate is for extracting neohesperidin and synephrine.
Hesperidin extracts
Get above-mentioned filter residue 100g, add water 2000ml, adds NaOH while stirring at 30 DEG C, stirs, and adjusts pH to filter after 11.0,1h; Get filtrate add appropriate dilute hydrochloric acid adjust system pH be 3.0, leave standstill 12h; 5-10 DEG C of crystallization, suction filtration, dries to obtain Hesperidin crude product.Add the methyl alcohol of 70% with solid-liquid ratio 1:60g/mL, react 30min, natural filtration at adjusting system pH to be 10.0,30 DEG C with dilute NaOH solution, then adjust filtrate pH to be 5.0, at 5-10 DEG C of standing 12h recrystallization with dilute hydrochloric acid; After recrystallization, filter, dry, obtain Hesperidin product, content of hesperidin is 95.15%, and yield is 4.06%.
Neohesperidin is extracted
Get filtrate and cross 001 × 7 strongly acidic styrene's type cation seperation column, collection of ions post effluent liquid, then washes with water.By cation seperation column effluent liquid and water lotion mixing, cross D101 macroporous adsorptive resins, wash washing, 20% methanol wash successively with water, then use 70% methanol-eluted fractions.Collect 70% meoh eluate, be condensed into medicinal extract.In medicinal extract, add the ammonium sulfate/solid sodium chloride of 5% massfraction, heat while stirring, stop heating after boiling, cooling, at 5-10 DEG C of crystallization 12h, obtains neohesperidin crude product.Neohesperidin crude product is placed in the beaker of clean dried, in beaker, 70% methanol solution is added with the ratio of solid-liquid ratio 1:5g/mL, stir evenly, put into electric mantle to be heated to boil, close electric mantle, add 6g gac while stirring, beaker is taken out after 10min, suction filtration while hot, cooling, at the off-white color needle-like crystal of 5-10 DEG C of crystallization; Suction filtration, dries, obtains neohesperidin; Recording purity through HPLC is 98.05%, neohesperidin yield 2.15%.
Synephrine extracts
Get pre-treatment filtrate and cross D101 macroporous adsorptive resins, washing, collect effluent liquid and water lotion, be concentrated into medicinal extract, suction filtration is carried out under diatomaceous assisting, filtrate joins 001 × 7 strongly acidic styrene's type cation seperation column after pretreatment, entering post amount is 2BV, effluent liquid is released with flow velocity 2BV/h, again with 2BV deionization washing resin column, release water lotion, 1.5BV1.5mol/L ammoniacal liquor wash-out is added in resin, flow velocity is 1BV/h, collect ammoniacal liquor elutriant, concentrated, being adjusted to pH value with HCl is 3.0, after D101 macroporous resin column, use ammoniacal liquor wash-out, get elutriant concentrated after, 5-10 DEG C of placement, crystallization, obtain crude product, be the HCl dissolving of 3.0 by crude product pH, then be 10.5 with ammoniacal liquor adjust pH, then concentrate, cooling, recrystallization at 5-10 DEG C, gained crystal is synephrine product. and in this product, synephrine content is 90.60%, and yield is 2.65%.
Claims (4)
1. from peel of Citrus reticulata Blanco, fruit, extract a method for Hesperidin, neohesperidin and synephrine, it is characterized in that: adopt following processing step:
The pre-treatment of A bigarabe dried immature fruit of citron orange fruitlet
With the dried immature fruit of citron orange fruitlet of bigarabe third time physiological fruit drop for raw material, drying, pulverizing, sieve, and uses 35-50% aqueous ethanolic solution, carries out seepage pressure effects 10-12h at 40-45 DEG C; Be added into polygalacturonase in the ratio of 0.01%-0.1%, stir 30min at 40-50 DEG C, then temperature regulating to 70 DEG C, process 15-30min; Then filter, the dregs of a decoction obtained are for extracting Hesperidin, and filtrate is for extracting neohesperidin and synephrine;
B Hesperidin extracting and developing, purifying
Be NaOH or Ca(OH of 10.0-11.0 by pH value)
2soak the dregs of a decoction, extract 0.5-1h; Filter, obtain extracting solution;
It is 2.0-3.0 that gained extracting solution HCl is adjusted to pH value, 5-10 DEG C of placement, and precipitation;
Throw out is washed with water to neutrality, then uses 70% dissolve with ethanol, 5-10 DEG C of placement, crystallization; Obtain Hesperidin crude product;
Hesperidin crude product is added the low-carbon alcohol of 70% with the ratio of solid-liquid ratio 1:60g/mL, adjust system pH to be 10.0-11.0 with dilute NaOH solution, at 30 DEG C, react 30min, natural filtration, then adjust filtrate pH to be 4.0-5.0, at 5-10 DEG C of standing 12h with dilute hydrochloric acid, recrystallization, obtains Hesperidin product;
C neohesperidin extracting and developing, purifying
Get filtrate described in steps A and cross strongly acidic styrene's type cation seperation column, wash with water;
By cation seperation column effluent liquid and water lotion mixing, enter D101 macroporous adsorbent resin; After washing, first with 20% low-carbon alcohol washing, then use 70% low-carbon alcohol wash-out;
70% low-carbon alcohol elutriant is concentrated, 5-10 DEG C of placement, adds (NH in the ratio of concentrated solution 5.0%
4)
2sO
4/ NaCl helps and analyses, and obtains neohesperidin crude product;
Neohesperidin crude product is added 70% low-carbon alcohol in the ratio of solid-liquid ratio 1:5g/mL in beaker, heating, filtration, cooling, recrystallization below 5-10 DEG C, obtains neohesperidin;
The extracting and developing of D synephrine, purifying
Get the filtrate described in steps A, being adjusted to pH value with HCl is 1.0, crosses D101 macroporous resin column, and washing is collected effluent liquid and water lotion, concentrated; Add diatomite filtration, filtrate is crossed 001 × 7 cation seperation column, entering post amount is 2BV, releases effluent liquid with flow velocity 2BV/h; Again with 2BV deionization washing resin column, release water lotion, in resin, add 1.5BV1.5mol/L ammoniacal liquor wash-out, flow velocity is 1BV/h, collect ammoniacal liquor elutriant, concentrated, being adjusted to pH value with HCl is 2.0-3.0, after D101 macroporous resin column, with 1.5mol/L ammoniacal liquor wash-out, get elutriant concentrated after, 5-10 DEG C of placement, crystallization, obtains synephrine crude product; Be the HCl dissolving of 2.0-3.0 by synephrine crude product pH, then be 10.0-11.0 with ammoniacal liquor adjust pH, then concentrate, cooling, at 5-10 DEG C of recrystallization, gained crystal is synephrine.
2. method according to claim 1, is characterized in that: described in step C, strongly acidic styrene's type cation seperation column is 001 × 7 cation seperation column.
3. method according to claim 1, is characterized in that: described macroporous resin is D101.
4. method according to claim 1, is characterized in that: described low-carbon alcohol is methyl alcohol or ethanol.
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| CN106083940A (en) * | 2016-07-11 | 2016-11-09 | 湖南华诚生物资源股份有限公司 | A kind of method extracting high purity novel aurantiamarin from Fructus Aurantii Immaturus |
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| CN107954883A (en) * | 2017-12-05 | 2018-04-24 | 贺州学院 | A kind of method that synephrine is extracted from ripe navel orange pericarp |
| CN109796507A (en) * | 2019-02-25 | 2019-05-24 | 涟源康麓生物科技有限公司 | The aurantiamarin remaking the preparation method of aurantiamarin and being prepared |
| CN109796507B (en) * | 2019-02-25 | 2020-12-25 | 涟源康麓生物科技有限公司 | Preparation method of reconstituted hesperidin and hesperidin prepared by preparation method |
| CN111777653A (en) * | 2020-08-21 | 2020-10-16 | 江西海富生物工程有限公司 | Preparation method of pure natural high-content neohesperidin |
| CN111777653B (en) * | 2020-08-21 | 2023-07-21 | 江西海富生物工程有限公司 | Preparation method of pure natural high-content neohesperidin |
| CN112047846A (en) * | 2020-10-13 | 2020-12-08 | 四川大学 | Method for extracting synephrine, naringin and neohesperidin from immature bitter oranges by using ultrasonic-assisted aqueous two-phase system |
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Denomination of invention: A Method for Extracting Hesperidin, Neohesperidin, and Synephrine from Orange Peel and Fruit Effective date of registration: 20231027 Granted publication date: 20181113 Pledgee: Bank of China Limited by Share Ltd. Guilin branch Pledgor: GUILIN SANLENG BIOTECH Co.,Ltd. Registration number: Y2023450000133 |